Process of and apparatus for treating shale and the like



Oct. 16, 1928,. 1,687,763

w. H. HAMPTON PROCESS OF AND APPARATUS FOR TREATING SHALE AND THE LIKEOct. 16, 1928. 41,687,763

w. H. HAMPTON Pnocsss oF AND APPARATUS FORv TREATING sHALE AND THE LIKEFiled Dec. 11. 1919 2 sheets-sheet 2 anw/nica (Patented 16, 19h28.

UNITED STATES wrnnmm mmrnmr summon, or New or Aim Arriiasruslron mirarmesnare am) man zum.

PRGCESB resigns PATNT orion.

YORK, N. Y.

Application filed December 11, 1919. Serial No. 344,618.

This invention relates to .Jrocesses of and apparatus fontreating sha eand thel like; and iteomprises more particularly a process of andapparatus for digesting bituminiferous solidsfsuch as shale or the like,with a hydrocarbon oil to extract valuable lbituminous matter therefrom,andv refining the digestion products in a systematicand economicalmanner, as hereinafter set forth.

In accordance with the process of the invention, the shale or otherbituminii'erous solidv to be treated is thoroughly digested inlinelydilvlded condition with an oil admixed therewthLthe digestionbeing conducted at Ti temperatures sufliciently high to effect sub- Ywhich remain mixed with residua then filtering and was Ishales, sands,ctc.

stantia'll'y'complete liquefaction and solution of i' ie bitumenspresent in the shale. Dun. in the digestion, certain -oil fractionsdist' eff and these vaporized fractions are conducted directly torefining apparatus for fur- Ttlitn treatment.' The heavier fractionswhich lare'not volatlized during the digestion and solid mineralmatter'are then subjected to suitable treatment for separation of suchresidual mineral matter, most desirably by diluting the mixture with ali hter oil fraction, and

iing in centrifugal apparatus. The mixture of oils thus obtained maythen be further treated for separation into desirable commercialfractions.

W'hile the process of the invention in its broader aspects concernedwith the recov er)7 of valuable hydrocarbons from bituminiferous solidmatter generally,it is especially applicable to the treatment ofoil-bearing For the sake of a concrete example to illustrate more fullythe underlying principles of the invention, the treatment of shale inaccordance with the presentl process will be more particularlyhereinafter described; aud novel apparatus especially suitable forcai'ryin r out such treatni'ent of bituminous shalc Wiil als bedescribed, although it is to be understood thatthe process may becarried out in apparatus differing in many particulars from that hereshown for purpose of illustration. y

Referring to the accompanying drawings which show more or lessdiavframmatically one system of apparatus'in which the novel process maybe practiced.

Fics. 1 and 2`v which are to be considered together, but which are forconvenience placed ou separate sheets, iilusirate a. complete sysand'shall have the proper degree of tem. in side elevation parts beingshown in section.

' In carrying out the resent process of treating shale with the aid ofthe apparatus here illustrated, more or less finely crushed oil-bearingshale, is fed from a supply bin l0 by conveyor ll, to a combined mixerand heater 12, to which a suitable extraction or digestion oil issimultaneously fed from either of two storage tanks 13, 14, throughsupply pipe 15 which includes a preheating coil 16, suitabl disposedwithin an enlargenient 17 of the ue 18, through which liuc pass hotgases from the furnace 19 of the heater 12. The preheated digestion oilthus fed to the mixer may vary Widely in character, but ordinarily it ismost convenient and desirable to employ a relatively heavy oil, such asa strippedl oil, that is, an oil from which the lighter fractions havealready been removed by some distillation method. Heavy residual oilsfrom practically any source are suitable, however; and in one especialldesirable embodiment of the invention, to e more fully referred tohereinafter, crude petro leuni serves as the di estion oil to be mixedwith the crushed shale in combined heater mixer .12. The pro ortion ofoil'used may vary considerably; gut in a typical example, a out equalvolumes of shale and oil give a satisfactory mixture. W'herc thedigestion oil initially mixed with'the crushed shale contains lightfractions, as in the case of crude petroleum hereinafter referred to, alarger quantity of oil is added at the outset in Order that the residualmixture obtained after the digestion treatment is completed iiuidity.

In the present specific example, the crushed shale and oil arethoroughly mixed by means of suitable agitator means such as helicalconveyors 20, so arranged Within the mixer 12 as to' advance the mixturetoward the discharge end of the mixer, whence the mixture passes throu hdischarge conduit 21, into a grinding device 22, which may be of anappropriate type'hut which is most desira ly a ball or tube mill,provided with a heat insulating housing 23. In this grinder the mixtureofushale and oil, Jwhich should be at a temperature of aroundSOO degreesF. or somewhat higher for best results, in the grinder until the'shale'has lbeen ulverized to the necessary extent. The liner the grinding, thebetter. Ir practice, it has the .mixture is gradually brought toatemperature of between 500 and 700 degrees F., .temperatures of about665 to 67 5 degrees F. in final'retort 27, ofthe series, being goodpractice. Each of these digesters is provided with means such as a screwconveyor 28, for gradually advancing vthe' fh1id mass through thedigester system and preventing accumulation of solid materials onthebottomv ofthe' retorts. Y Materialpassesfrom digcster to digester 2 6through a suitableeonduit 29, and a similar conduit affords connectiontween digesters-Zand 27, while suitable furnace means 29 provide thenecessary heat for the -di-gesters. The vapor olf-takes 31 of thedigesters may all lead into a common vapor main 32 Steam or an inert gasmaybe introduced into the mixture undergoing digestion, or caused tosweep =over the surface thereof, to facilitate Avaporization of certainfractions at a lower temperature thap would be `otherwise required totvolatilize them. Through these olf-takes pass the vapors of thosefractions of the oils inithe digesters that are volatilizable under'theconditions of operation, and thc'se vapors while still hot are mostdesirably conducted directly to trea-'ting vand refining apparatus forthe production of commercial fractons.- In the present example such`further treatment comprises superheating of' the' vapors in `thepresence of admixed steam, followed by fractional condensation. As hereshown, a steam injector 33 draws the oil vapors from 32 and forces themixture of Steam and oil vapors through 'coiled pipe superhcaters 34 and35, the mixture attaining ,considerably higher temperatures in thesesuperheaters than the maximum digestcr temp `iatures. VI'iere de'-sirable, the injectorjmay be operated to create subatmospheric pressureinV thel'digesters and thus 4to facilitate vaporizationtherein; and, asstated, steam may also he introduced into the digestion mixture or'bleu-Ii over-the surface to aid-in driving olf certain fractions.

In' practice the temperatures in, the superheaters may attain 900 or10000 F. or more, 1300" F. being attained in some cases. By thistreatment the heavier' portions 'of the volatilized oil fractions are toa grca .extent cracked or broken donn to give lighter fractions. Anytarrv products depcsited in the coils of the superheater may be trappedof through valved connections 36 into Aa common down pipe 37, whichleads to a collection tank 38, from which the collected Aheavy productsmay be removed through valved outlet 39 conducted to. supply tanks 13,14, in any convenient manner, orotherwise. disposed of.l The highlyheated vapors leaving the superheater at 40, pass througha cooling andcondensing system, shown here-as comprising two chambers 4l andr42,',hvut which may "comprise as many chainbersis'imay .be

desirable, wherein certain relatively heavy fractions which may still bepresent in the vapors, together with more or less-water, are condensedout and dropped to the bottom of the chambers. By suitably 'desigxiin"the chambers 41 and 42, and properlyreguiixting the operatingconditions, lubric'atin and the heavier kerosene fractionsA may e;fractionated out in these chambers. .The vapors leaving chamber 42, and-containing some kerosene fractions and still lighter fractions, arethen most desirably subjected'toj alwashing treatment. In the presentexample the vapors from chan'iber 42 passdown through pi pe 41j whichdips below the surface of Water contained in f wash tank 44. This treatment remoxf' resinous and.. other matters which would tend todiscolo-rsucceeding con densed fractions, and a part ofthe kerosene mayalso .collect there and be drawn ofi through outlet 44, The washedvapors leave the Wash tank through pipe 45 and are led through anotherseriesof cooling and condensing chambers 46, 47, ,of Which-there ma): beany desired number, similar in character to 41 and 42. Here such` 'of'.the -lighter kerosene as may have been .carried over, and gasolinefractions, are condensed, while the so-called incondensible or fixed'sesleaive the system at 48, and are dispos y "of in'an'y suitablemanner. Theyario'us -fr'actionsdeposited in the series of coolingandcondensjing chambers may outlets 49 and led to separate storage com'tainers not shown). It will beunderstood that the series ofcooling-,chambers mayv comprise more than the four units shown, the'number used depending upon the'extent to which it is desired 'v toCarryfraCtiOnat-iOn. The heavier fractions thus obtained from the vaporsfrom the digesters may 'be rlubricating fractions, and, ifdesired,va,.part of such be marketed, or part, especially Alu the.presentv digester and dips below the level of the liquid therein which,as shown, should be maintained considerably above the upper limits ofthe screw conveyer 28. The small iso lated va por space 51 thus formedbetween the batile plate and the adjacent end of the digester is tappedby a vapor ott-take 52 which leads to a small condenser 53. This comdenser maf)7 be provided with pee holes or observation windows (notshown whereby the amount of condensate collecting therein may be'readily observed and measured.' The rapidity with which condensatecollects therein being observed, a measure is thus. had of the progressof the digestion. If condensate collects at an abnormally rapid ratethis indicates that the oil mixture arriving at the dischar eend of thedigested system has not been sujected to the heat treatment for thenecessary length of time',

conveyer mechanism and thus pro time required for the shale and oilmixture to pass through the system.

From the last digester 27,'the still fluid residual mixture of heavybitumens and fixielyl divided solid mineral matter is discharged t roughoutlet pipe 54 inte a cooling device '55 which may be generally similarin character to Ithe digester but is not provided with heating means.'fixe mixture is moved at the proper adjustable rate through the coolingapparatus lay-conveying means such as screw conveyer 56, and gives up alarge proportion of its heat to vrelatively cool oil flowing throughcoils"57 and 58 and derived from a later sta-ge of the process, as willbe hereinafter more fully explained.

The mixture of residual heavy oils and mineral matters having been thuscooled down suiiciently, most desirably to around 200 F. or thereaboutsit mayv then be diluted with a. lighter oil fraction, such as keroseneVfor example, without occasioning undue volatilization of the mixture. Accordingly the mi ture passes from the cooler or heat-exchanger 55 into amixer 5S, into the top of whichis also introduced through valve pipe 59,kerosene or the-like whichis supplied from a storagetank 60, In practiceit is desirable to dilute with at least an equal volume of'kerosene. Theprovision of battles 61 or the like in the miximg` chamber 58 ensuresthoroughniinh'ling of the dilucnt oil with the heavy i'nix'tz-xre "ofresidual oil andV mineral matter. From the resultant diluted mixture,which maybe at a tempera ture considerably below Q00 F., the Acontainedsolids may then be .separated in any suitable manner; but in view oi thery finely divided condition of the .solid matter, it is moet desirableto make the separat .n ccntrifllgally und to this: rnd the dilutedmixture is led through pipe (32 into a centrifugal filtering device 63,the separated liquid por- `changer 55, to

whereupon this con- 'dition can be remedied by slowing down the ongingthe p tion of the mixture passing.; thence through pipe-64 into astorage tank f1.5. The relativiA ly cool oil collected in (55 containsboth heavy and light fractions, into which it can be sepa rated by anyconvenient method of fractiona4 tion. In the best embodiment of thepresent process, part or all of the heat requirwl lor fractionationobtained by utilizing,l said cool oil as the cooling medium in the heatex- Y reduce the temperature of the heavy residual mixture leaving thedigester l27. To thi."l end oil is pumped from 65 through pipe 66 firstinto tlte aforementioned pipes 57, arranged outside of and adjacent thebottom and sides of the heat exchanger and thence through the pi ing 58which is immersed in thc body of oilp'eontained in the cooler. Theoutside piping 57 is of course arranged in goed heat conducting relationto the shell of the heat exchanger, loss ot heat to the atmospherebeing'guarded against by means of insulation lagging 67.

From the heat exchanger, the oil which has assed through coils 57 and 58and thereby as become relatively highly heated by absorption of heatfrom the residual digestion mixture new conducted to suitable frac*Mounting-apparatus for separating into de sired fractions, beingadditionally heated vn any suitable manner en route if necessary, inorder tobring it up tothe particular topping; temperature deemednecessary, say 6o() F. or somewhat higher, in a typical instance. In thepresent exampie, the hot oil leaning the heat cxchanger'through pipe 68is simply sprayed into the upper part of a topping tower 69, the heavierfractions collect-ing at the bottom of the tower, and being pumpedtherefrom through pipe 7() to th: .ill storage 13, 14, for adinxturewith more crushed shale. rl`he vapors set free in the topping tower 69and remaining uncondensed, pam out through off-take 7l into one or morecondensing chambers 72., in which light fractions may he condensed andcollected in any com venient manngr.

The separated solidv matter collected on the revolving filter screen ofthe centrifugal device may be Washed free of adherent heavy oils byWashing with gasoline or other light .Washing .solvent lsupplied throughpipe 725 from storage vessel 74.-. The wash oil thus obtained may bepassed into a separate receiving'tank 75 with which pipe 64 isconnected, the valves shown in the piping system being manipulated topermit this. This wash oil is of suitable character to beused fordiluting the digestion mixture and it may accordingly be pumped to tank6() through pipe I76. The Washed solid material remaining on' the.screc`n of the centrifugal 63 may be dropped through hopper 77 into adrier 78 to recover therefrom any gasoline or the like which may adherethereto from the washing. Gasoline or other light vapors lli fl i Iii.

thus obtained may be led off through pipes 79 to a condensing system(not shown), while the. dried solid material is discharged at 80, andmay or may not be further treated to recover additional portions ofbituminous matter remaining therein.

It Will be observed that in the process above describe-d, noi only doesthe oilv initially mixed with the shale act as a solvent or liquetyingagent for the shale l`tumens, but both it and said ,bitumens undergo,during theheat digestion-rL certain amount of fractionation by straightdistillation, version or transformation of a part of the heavyhydrocarbons into lighter, to an extent depending largely upon thetemperature and duration of digestion, both ot which are easilyregulable and controllable. No draf-.'- tic cracking occurs in thedigestion, however, and practically no lcoke is formed or free carbonseparated. The digestiod vapors being immediately subjected without lossof 'contained heat units, to cracking treatment, followed byfractionation largely into light commercial products, a high degree ofeconomy is made possible by this combined digestion and refiningprocess. The employment of steam in cracking the digestion vaporssubstantially prevents formation of -free carbon or coke in that part ofthe process, thus enabling continuous operation ot the complete processover long periods.

Vhere crude petroleum is employed, wholly or in part, for admixture withthe shale to be digested, the benefits ot the invention can be realizedto the fullest extent; for the novel process permits accomplishing in 1,com ylined procedure both distillation and fractionation of petroleumand extraction and separation of shale bitumens in a highlyadvantageicni` and efficient manner. Employing crude pe roleum as thedigestion medium, a somewhat larger proportion should be used in mixtureWith the shale than where a Stripped oil or other heavy fraction orresidue is use because it is necessary to allow for the distillationloss during digestion. It may also be advisable, when using crudepetroleum, to return to the system a smaller proportion, or even none,of the heavy tractions obtained at later stages, since under thesecircumstances and also a. mild eou-` it may be more economical to refinesuch heavy fractions entirely by other n'iethods in order to permithandling the maximum amount of crude petroleum in the combined proceduredescribed.

W'hat I claim is:

l. The process ot obtaining valuable products from shale likebituminiferou's solids which comprises digesting suh a shale-likebitiuninit'erous solid in `finely divided condition with a heavy mineraloil at temperatures between 500 and 700 F., mixing steam with theevolved vapors and Subjecting the mixture to cracking treatment at h'"her temperatures, flactionally condon 'ing the products of cracking,diluting the res mual digestion mixture with a lighter oil, separatingsolid matter from the diluted mixture, treating the residual oil toobtain a heavy traction therefrom, and utilizing such heavy fraction anda heavy fraction obtained from the aforesaid cracking products Ifordigestion of a further portion 'of shale or other bituminiterous solid.Y

2. The process of obtaining. valuable hydrocarbon products whichcomprises digesting a mixture of shale-like bituminiferous solid matterand a mineral oil with the aid ot heat, cooling the digestion mixture,separating' solid mattei' from the cooled digestion :'nixturc andthereby obtaining liquid bitunriniterous material, employing such liquidmaterial in theatoresaid cooling ot the digestion mixture, therebyheating said liquid material, Aand thf-t: fractionating said liquid 3.Apparatus ot the character described comprising the combination with adigestion chamber. of a heat exchanger, conduit means -arranged toconduct unvaporized material from said digestion chamber to said heatexchanger, means 'for separat-ing solids from liq'iiids, conduit' meansarranged to conduct cooled material from said heat exchanger t0 suchseparating means, means for conducting separated liquid from suchseparating means to said heat exchanger, fractionating means, and meansfor conducting said'separated liquid from the heat exchanger to saidfractionating means.

In, testimony whereof I hereunto aix my signature.

"Wit/I. HUNTLEY HAMPTON.

rial, at a suitable topping temperature.

